Amino alcohols

ABSTRACT

Compounds of the formulas   INCLUDING PARTICULAR DERIVATIVES THEREOF, ARE PROVIDED. The subject compositions have utility in a wide variety of applications and their use as corrosion inhibitors for metals is exemplary.

United States Patent [191 Gipson Mar. 18, 1975 I AMINO ALCOHOLS OTHER PUBLICATIONS [75] Inventor: Robert M. Gipson, Austin, Tex. Chem. Abstracts 63:976lb (1965). [73] Assignee: Jefferson Chemical Company, Inc., Chem Abstracts 54:409d (1960) Chem. Abstracts 51:1552lh (1957). Houston, Tex.

Browne et al., J. Org. Chem. 17, 1187-93 (1952). {22] Filed: June 16, 1972 [2]] Appl NO; 263,552 Primary Examiner-G. Thomas Todd Attorney, Agent, or Firm-John R. Kirk, Jr.; Terrence Dean Dreyer; James L. Bailey [52] U.S. Cl. 260/247.7 A, 252/392, 260/268 R,

260/348 R, 260/534 R, 260/5709, 260/573, 57 ABSTRACT 260/584 R. 424/325, 424/330 1 d fth f u] 51 Int. Cl C07d 87/32 mpoun S 0 e as [58] Field of Search..... 260/247.7 A, 268 R, 573 R,

260/570.9, 293.9 3 Q 3 [56] References Cited zr UNITED STATES PATENTS R2 R4 R2 R4 1.541.088 2/1951 Nikawitz 260/584 2,569,549 10/1951 Barrick 260/543 2.856.363 10/1958 Brennan... 252/336 including particular derivatives thereof, are provided. 3.441.612 4/1969 Drew 260/584 The subject compositions have utility in a wide variety 1547.932 12/1970 Gerecht 260/294-7 of applications and their use as corrosion inhibitors for FOREIGN PATENTS OR APPLICATIONS metals 1S exemplary- 1.029.738 5/1966 United Kingdom 11 Claims, N0 Drawings AMINO ALCOHOLS BACKGROUND OF THE INVENTION SUMMARY OF THE INVENTION The invention is amino alcohols (which includes the salts. such as the sulfates, hydrochlorides, and the like; quaternary ammonium compounds; alkylene oxides; and amine oxides derived therefrom) of the formulas I or II wherein, individually, R and R are linear C -C alkyl groups, preferably C -C alkyl groups and R and R contain a total of eight to 38 carbon atoms; individually, R and R are (a) hydrogen or (b) are selected from alkyl, aryl, aralkyl, or alkaryl radicals, each radical containing from I to carbon atoms or (c) where R and R, are joined together to form a morpholine or piperazine ring; or (d) are the radical (CH ),,,[H- N"((H l,,, |,,-Z, wherein m is 2 or 3, n is l to 3 and Z is lH or ()H; and wherein the alkyl or aryl groups, or combinations thereof, comprising R or R individually can be substituted alkyl or substituted aryl groups containing hydroxyl, ether, amino, or carboxyl substltuents, or admixtures thereof. For example, individually, R and R, can be selected from CH CH- CH- d or CH CH NH- CH -CH NH and the like. Preferably, R and R are individually selected from methyl, ethyl, hydroxyethyl, hydroxypropyl, aminoethyl, aminopropyl, or benzyl radicals.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The amino alcohols of the invention are prepared by reacting epoxides of formula III 2 (III) R1 C-CH2 0 with amines of formula IV wherein R R R and R are as defined in the summary of the invention, above.

Exemplary amines of formula IV include, for exam ple, ammonia, methylamine; dimethylamine; diethylamine; dipropylamine; dibutylamine; ethylenediamine; 1,3-propanediamine; diethylenetriamine; triethylenetetramine; hexaethyleneheptamine; imino-bispropylamine; ethanolamine; diethanolamine; aminoethylethanolamine; aniline; benzylamine; piperazine; morpholine; and the like.

Suitable epoxides conforming to the above formula III can be prepared according to copending US. Pat. application Ser. No. 263,678, filed June 16, I972, entitled 2,2-Dialkylepoxides, by Robert M. Gipson et al., which disclosure is incorporated herein by reference thereto.

As hereinbefore stated, my invention includes the salts, quaternary ammonium compounds, alkylene oxides, and the amino oxides that are derived from particular amino alcohol compositions of this invention.

In most instances these derivatives can be prepared directly, i.e., without having to perform a separate recovery step to isolate the amino alcohols of this invention. It is sometimes preferable, however, to separate the amino alcohol products of this invention before proceeding to prepare these derivatives of my invention as hereinafter described.

The novel alkylene oxide compositions of this invention are dervied by reacting alkylene oxides that contain preferably from two to four carbon atoms per molecule with certain amino alcohols of this invention that conform to formulas I or II above provided however that at least one of said R or R,, as hereinbefore defined, is the radical (CH ),,,[HN-(CI-I ),,,],,Z, wherein m, n and Z are as hereinbefore defined. Preferably, one of R or R is hydrogen.

Accordingly, alkylene oxide compositions are provided that conform to the following illustrative formulas 1 5 1: I R5 2" r HO-CHg-C-N 2 R6 R2 R6 wherein, individually, R or R are (a) the same as R or R,, as hereinbefore defined except that R and R are not hydrogen, or (b) and provided that at least one of R or R is or (3) -OH,

and wherein R is as previously defined.

Alkylene oxides such as ethylene oxide; propylene oxide; isobutylene oxide; 1,2-epoxybutane; 2,3- epoxyhutane; or admixtures thereof; are representative of preferred oxides useful in preparing our novel alkylene oxide compositions. The alkoxylation reaction can be conducted using conventional methods and conditions such as temperatures within the range of about 40 to 200C, and pressures from about 0 to 100 psig. Representative procedures are described in the following reference which disclosure is incorporated herein by reference thereto. Martin J. Schick, Ed., Nuniunic .S'urfar'mnrs, Marcel Dekker Inc.. New York, 1967, pp 181204.

Likewise, novel amine oxide compositions are provided which can be illustrated by the formulas wherein R,. R- R and R, areas heretofore defined except that R and R, are not hydrogen. Accordingly. the novel amino alcohols from which the novel amine oxide compositions are derived are prepared using an amino alcohol of formulas l or ll provided however that R and R are other than hydrogen, Conventional procedures can be used to form the amine oxides such as procedures represented by D. B. Luke and G. L. K. Hah, J. Am. Oil Chem. Soc, 40, 628 I963 which disclosure is hereby incorporated by reference thereto.

The novel quaternary ammonium compounds that are derived from my amino alcohols can be illustrated by the following representative formulas R R3 R R3 \1 HO-C-CHg-N xor HO-CH2-CN x R2 R4 R2 R4 wherein R,, R R and R are as previously defined, and R represents (a) a C -C saturated or unsaturated aliphatic hydrocarbon radical such as ethyl, butyl, ally], and the like, (b) an aromatic hydrocarbon radical containing from six to 14 carbon atoms per radical, such as phenyl, benzyl, and the like, or substituted radicals of (a) or (b) having substituents thereon selected from hydroxyl, amino, ether or carboxyl, and admixtures thereof; and wherein X represents an anion such as the halides, e.g., chloride, bromide; hydroxide; methylsulfate; and the like.

The quaternary ammonium compounds ofthis invention can be prepared from my novel amino alcohols by conventional methods and conditions. For example, al kylating agents such as the primary halides, e.g., methylbromide. benzylchloride, or the like; dialkylsulfates, ethylene oxide; chloroacetic acid and the like, can be suitably employed for reacting with the amino alcohols of formulas l and ll to provide quaternary compounds ofthis invention. A representative preparation of quaternary ammonium compounds is described by Melvin .l. Astle. Ed.. Industrial Organic Nitrogen Compounds, Rheinhold Pub. Corp, N.Y., I961, which disclosure is incorporated herein by reference thereto.

The amino alcohols of this invention, as well as the amine oxides; alkylene oxides; and quaternary compounds derived therefrom, are useful as corrosion inhibitors for metals. The amino alcohols are also useful in preparing amphoteric compounds which demonstrate significant surfactant activities.

Likewise. the amine oxides, alkylene oxides, and quarternary ammonium compounds also demonstrate useful surfactant characteristics. Particular compositions have also been found to exhibit biological activi ties.

Unexpectedly, the activity characteristics of our compositions are such that they can be conveniently and advantageously utilized in widely varied applications. Also in view ofthe essentially linear nature of our compositions it was particularly astounding to discover that our compositions had extremely low freezing points and that they were essentially completely soluble in organic solvents. The amino alcohols of formulas l and ll, for example, are soluble in essentially all conventional organic solvents.

As herein described, novel amino alcohols are provided by reacting the epoxides of formula III with the amines of formula IV. Generally, this reaction can be conducted at temperatures within the range of about 60 to 200C. preferably from about to 180C. Times in the range of about 10 minutes to 72 hours can be employed and generally about 30 minutes to 10 hours is suitable. Pressures that are sufficient to maintain the reactants and products essentially in the liquid phase are preferred. lfdesired, an inert or nonoxidizing atmosphere can be maintained such as by employing nitrogen, methane, or the like in the reaction vessel. Aromatic and aliphatic solvents such as the alcohols, e.g., methanol, isopropylalcohol, and the like; ether; or chlorobenzene. and the like, can be conveniently employed although solvents are not required.

Although no catalyst is strictly necessary, mineral acid and halide acid salts of the amines of formula IV are suitable catalysts for the reaction between the epoxides and amines of formulas III and [V respectively. Thus, preformed acid salts can be suitably employed or the catalyst can be formed in situ by the addition of the mineral acid or halide acid, or admixtures thereof, to the vessel containing the reactants, i.e., the compounds of formulas Ill and 1V.

Mineral acids suitable for in situ catalyst preparation or for use in preforming the mineral acid salts of the stated amines are hydrochloric acid, sulfuric acid, and the like. Representative halide acids are HBr, HCl, HI, and the like.

Exemplary preformed acid salt catalysts are dimethylamine hydrochloride, ethanolamine bisulfate, triethanolamine hydrochloride, and the like.

Other preferred catalysts that can be suitably employed for preparing the subject amino alcohols include the Lewis acids. Exemplary are boron trifluoride, titanium tetrachloride, aluminum chloride, tin tetrachloride, and the like.

Other catalysts such as quaternary ammonium salts can also be used. Exemplary are as tetramethylammonium chloride, trimethyllauryl ammonium chloride. tetraethylammonium bromide, and the like. Alkali metal alkoxitlcs formed from lower alkyls. e.g., C to (I. such as sodium methoxide are another class of suitable catalysts. The mineral acid salts and the halide acid salts of the stated amines and the Lewis acids are the preferred catalytic material.

Although the amount of catalyst or catalysts used can vary widely, generally from about 0.00001 to 1.0 mol of the catalyst is provided per each mol of the amine compound (i.e., composition represented by formula IV Generally, the amine compound of formula IV is employed in an amount such that about 0.1 to mols of said amine compound is provided for each mol of said epoxide compound of formula [11. For convenient and economic processes, generally about stoichiometric quantities of the two reactants are represented by formulas Ill and l\' are employed.

lllustrative of the foregoing discussion and description, and not to be interpreted as a limitation on the scope thereof or on the materials herein employed, the following examples are presented.

EXAMPLE 1 A 250 ml three neck flask equipped with a stirrer, thermometer and reflux condenser was charged with 100 g morpholine, 4 ml concentrated hydrochloric acid and 50 g of a mixture of 1,2-epoxy-2-octyldecane and l.2-epoxy2-hexyldodecane. This mixture was stirred and heated at reflux l2830C) for hours. The reaction mixture was diluted with 300 ml benzene. This solution was washed twice with 200 ml 5% sodium hydroxide, dried over sodium sulfate and the benzene and excess morpholine removed in vacuo to give 61 g product. The infrared and nuclear magnetic resonance spectra showed the material obtained was predominantly compounds of the formulas HO-C -CH N (3 E1 CH CH CHg-CH EXAMPLE 2 A l-liter stirred autoclave was charged with g of epoxide consisting essentially of 1,2-epoxy-2- hexyldecane, 3 g tetraethylammonium bromide, 300 g tertiary butyl alcohol and 100 g ammonia. The autoclave was stirred and heated to l7882C for 3.75 hours. The pressure dropped from 1,400 to 1,040 psig during this period. The effluent was stripped of alcohol and the residue dissolved in 200 ml benzene. This solution was washed twice with 100 ml of water, dried over sodium sulfate, filtered, and the benzene removed in vacuo to give 98 g product. The product contained 2.92 milliequivalents per gram amine by titration. The infrared and nuclear magnetic resonance spectra showed the product to be a mixture of amines of the formulas HO-C-CH2NH2 HzN-C-Cl-IgOH EXAMPLE 3 A l-liter stirred autoclave was charged with g ethylenediamine, 100 g epoxide consisting essentially of 1,2-epoxy-2-butyloctane and 3 ml concentrated hydrochloric acid. The autoclave was pressured to 100 psig with nitrogen and heated at C for 4 hours. The reactor effluent was diluted with 150 ml benzene. The resulting solution was washed twice with 5% sodium hydroxide and once with water. The benzene was stripped and the residue distilled to give 95 g material, b.p. 140C at 0.5 mm Hg. The product contained 8.23 milliequivalents per gram amine (theory=8.20) and 4.06 milliequivalents per gram primary amine (theory=4.l0). The infrared and nuclear magnetic resonance spectra showed that the product was predominantly a compound of the formula EXAMPLE 4 A l-liter stirred autoclave was charged with 100 g l,2-epoxy-2-octyldodecane, 100 g dimethylamine, 3 g tetraethylammonium bromide, and 300 g t-butyl alcohol. The autoclave was pressured to 200 psig with nitrogen and heated at 160C for 4 hours. The effluent was stripped of alcohol and 200 ml benzene added to the residue. This mixture was filtered. The filtrate was washed twice with 100 ml 5% sodium chloride solution, dried over sodium sulfate, filtered and the benzene removed in vacuo to give 95 g of product. The product contained 2.70 milliequivalents per gram amine. The infrared and nuclear magnetic resonance spectra EXAMPLE 5 A l-liter flask equipped with a stirrer and a condenser were charged with 150 g 1,2-epoxy-2- octyldodecane. 150 g diethylenetriamine and 5 ml con centrated hydrochloric acid. This mixture was stirred and heated at 160C for 3 hours. The effluent was washed once with 100 ml of water and twice with 200 ml 5% sodium hydroxide. dried over sodium sulfate and filtered. The filtrate was passed through a wiped film evaporator at 160C and 0.2 mm Hg pressure. The bottoms were reflashed at 250C and 0.2 mm Hg to give 130 g overhead (product) and 41 g bottoms. The overhead contained 7.15 milliequivalents per gram amine. The infrared and nuclear magnetic resonance spectra showed that the product was predominantly a compound of the formula C Hl7 30 lO Zl EXAMPLE 6 The product from Example 5 above was reacted with ethylene oxide at lZ-30C to give a product containing 6.73 milliequivalents per gram hydroxyl groups and 4.73 milliequivalents per gram amine.

EXAMPLE 7 A 500-ml flask equipped with a stirrer. condenser and nitrogen purge was charged with 150 g ofa mixture of l.2epoxy-Z-hexyldodecane and 1.2-ep0xy-2- octyldecane, 150 g diethanolamine, and 3 g ammonium chloride. This mixture was stirred and heated at 160C for 4 hours. The reaction mixture was cooled and 100 ml benzene and 100 ml 592 sodium hydroxide solution were added. The organic layer was separated, washed three times with 100 ml sodium hydroxide solution. dried over sodium sulfate, filtered. and stripped of benzene in vacuo to give 195 g viscous liquid product. The

EXAMPLE 8 A l-liter flask equipped with a stirrer, condenser, and thermometer was charged with 100 g iminobispropylamine. 100 g dichlorobenzene and 5 g ammonium chloride. This mixture was heated to 180C and 100 g 1.2-epoxy-2-decyltetradecane was added over a 35-minute period. The temperature was maintained at reflux 187-89C) for an additional 1 hour. The rcac tion mixture was cooled to room temperature and 200 ml of sodium hydroxide solution was added. The organic layer was separated. dried over sodium sulfate and filtered. The filtrate was passed through a wiped film evaporator at 200C and 0.1 mm Hg pressure to remove solvent and unreacted starting material and give 109 g product (as bottoms). The product contained 5.03 milliequivalents/g amine. The infrared and nuclear magnetic resonance spectra showed that the product was predominantly a compound ofthe formula ca na-ca ca ca ua EXAMPLE 9 The product from Example 8 was reacted with ethylene oxide (excess), at 1 10C to give a product containing 2.07 milliequivalents/g amine.

EXAMPLE 10 EXAMPLE 1] A glass pressure bottle was charged with g of the N.Ndimethylaminoalcohol of the formula g pentane and 15 g methyl bromide. The reaction mixture was stirred and heated at C for 3 hours. The bottle was cooled and vented. The precipitate was filtered. washed with pentane and dried to give 21 g of white crystalline material. Analysis for bromide (\'olhard): found 20.6i; theory. 21.0%. The infrared and nuclear magnetic resonance spectra showed the structure to be a compound of the formula HQ-C-CH 1| 1-CH 3 c a CH3 EXAMPLES l2l6 Some of the representative compositions that were likewise prepared according to the method of Example ll include the following compositions which are described in illustrative fashion 3 HO/C-CH 17- R x' Example No. R R R R R, X

l 2 decyl octyl methyl methyl benzyl C] l} octyl hexyl methyl methyl allyl Cl l4 a )decyl decyl methyl methyl methyl Br h Jdodecyl dodecyl methyl methyl methyl Br [5 a octyl octyl methyl methyl methyl Br h ldecyl hexyl methyl methyl methyl Br lo octyl hexyl methyl methyl methyl Cl 11 mnturc ul (it) and (h) In further exemplification of our novel compositions and demonstrative of their varied activities the composition of Example I l was tested for surface active propcrties. it was found to demonstrate a Draves wetting time of less than one second using a 1.5 gram hook at 0.25% concentration. The composition of Example 13 was tested for biological activity and found to be a post emergent herbicide, a mildewcide against erysiphe polgom' and was also effective in inhibiting the growth of smpliylomu-us aureus. The composition of Example 14 was tested in the Ross Miles foam height test and demonstrated as initial foam height of I85 and a five minute foam height of 165. The composition of Example 15 demonstrated exceptional foaming power as determined by said Ross Miles test and demonstrated foam Wt Loss heights of 233 initial and 208 after five minutes. The Example l5 composition had a Draves wetting time of 3 seconds and 33 seconds at 0.1 and 0.05% concentration, respectively. using a 3.0 gram hook. This composition also exhibited biological activity as a post emergent herbicide. mildewcide (both topical and systemic) and functioned as an aphicide. The composition of Example it was tested for metal corrosion inhibition and it was found effective.

EXAMPLE 17 A solution of 50 g of the amino alcohol of the formula 'was filtered and the solvent removed at reduced pressure to give the amine oxide of the following formula containing only 0.03 milliequivalent/g free amine.

C H 0 ca 8 17 3 /Ho-c-cH -n E 13 CH3 Results comparable to those disclosed in the examples are obtained when other compounds within the scope of the invention but not illustrated are prepared.

The compounds of the invention, as before stated, are useful in a variety of applications including useful ness as corrosion inhibitors for metals. in demonstration thereof, corrosion tests were carried out as follows. Test coupons of mild steel were buffed, washed with soap and water, rinsed in water, then acetone, and dried and weighed. The test coupons were placed in bottles containing the desired level of inhibitor, 14 ml kerosene and ml synthetic brine (5.0% NaCl, 0.5% CaCl 0.06% acetic acid, saturated with CO A control with no inhibitor added was used in all tests. The bottles were placed on the outer perimeter of a 22 inches wheel which was turned at 37 rpm for 72 hours. The coupons were washed with soap and water, rinsed in water, then acetone, and dried and weighed. The percent protection given by the compounds of my invention was calculated by of Control Wt. Loss of Coupon X Wt. Loss of Control bromide. l'he foregoing mixture was heated at 160C for 1 hours. The reactor effluent was then stripped of lSOprOp YlfllCOhUl solvent and excess amine, and filtered to give 342 grams of product containing 5.94 meq/g amine. A slurry ofZZ grams of maleic anhydride in 150 ml benzene was stirred under nitrogen while 75 grams of the above prepared amine was added thereto. The mixture was heated for 1 hour at 50 to 55C and then cooled to room temperature.

The product was precipated by the addition of 100 m1 of pentane. After two recrystallizations from benzenepentan, 68 grams of the maleic amide, represented below was obtained.

C H Cf 1. An amino alcohol of the formula HO-C-CH -N wherein R, and R are C to C alkyls and R and R are selected from methyl. ethyl, hydroxyethyl, hydroxyprop) l. aminoethyl. aminopropyl or benzyl or one of R and R is hydrogen.

2. A compound according to claim 1 of the formula R2 CH 3 3. A compound according to claim 1 of the formula R1 CHZCHZOH R2 CHZCHZOH 4. A compound according to claim 1 wherein one of R, and R is hydrogen.

5. A compound according to claim 4 of the formula aoc CH --NHCH 6. A compound according to claim 4 of the formula 7. An amino alcohol of the formula HQ-p-CH -NH- (CH [HN- (c11 ];z

wherein R and R are C to C alkyls. m is 2 or 3. n is l to 3 and Z is NH- or OH.

8. A compound according to claim 7 of the formula 9. A compound according to claim 7 of the formula 10. A compound of the formula wherein R and R are alkyl containing a total of 16 carbon atoms. 

1. AN AMINO ALCOHOL OF THE FORMULA
 2. A compound according to claim 1 of the formula
 3. A compound according to claim 1 of the formula
 4. A compound according to claim 1 wherein one of R3 and R4 is hydrogen.
 5. A compound according to claim 4 of the formula
 6. A compound according to claim 4 of the formula
 7. An amino alcohol of the formula
 8. A compound according to claim 7 of the formula
 9. A compound according to claim 7 of the formula
 10. A compound of the formula
 11. A compound according to claim 10 of the formula 